模板法制备的掺镧氧化镍多孔空心微球及电化学电容性能

采用模板法在水热条件下合成了掺La的NiO多孔空心球。采用X射线衍射(XRD)、X射线光电子能谱(XPS)、扫描电镜(SEM)、透射电子显微镜(TEM)和X射线能谱(EDS)对其结构和形貌进行了表征。采用循环伏安、恒流充放电技术对其电化学性能进行了测试,研究结果表明,La掺杂对NiO空心球的粒径、壳层厚度和电化学性能均有显著影响,当La掺杂量为1.30mol%时,掺杂后NiO的单电极比电容达到205 F.g-1,比未掺杂的提高了50%,并且表现出良好的循环稳定性和可逆性。     

稀土镧掺杂MnO2电极的制备及性能研究

以Mn(CH3COO)2·4H2O为原料,利用直流电沉积法合成MnO2电极材料,在制备过程中向溶液中添加h(NO3)3·6H2O对MnO2电极进行改性.分别采用X射线衍射(XRD)、扫描电子显微镜(SEM)和原子吸收方法分析了电极的结构、形貌以及组成.通过BET分析,发现掺La后MnO2的比表面积明显增大.采用循环伏安(CV)和恒流充放电技术测试了MnO2的电化学性能.结果表明,MnO2比容量为198.72 F·g-1,掺La后MnO2的电化学性能显著改善,其比容量为276.60 F·g-1.     

NiO/CNTs的制备及其电化学电容行为研究

用改良的沉淀法在酸化处理过的碳纳米管(CNTs)上沉积氢氧化镍, 经300 ℃热分解得到NiO/CNTs复合电极材料. 采用X射线衍射(XRD)、热重分析(TGA)、扫描电镜(SEM)和Brunauer-Emmett-Teller (BET)比表面积分析等方法对合成的材料进行了物理表征|用循环伏安法和充放电测试对其电化学性能进行了研究. 结果表明, CNTs的引入在一定程度上提高了NiO的分散性, 从而大大增加了复合电极材料的比电容和倍率容量. 掺入20% CNTs后复合电极的比电容达到最高值(309 F•g^－1)|掺入40% CNTs的复合电极材料扣除CNTs对容量的贡献后(本实验测试CNTs的比容量为35 F•g^－1), NiO的放电容量可达420 F•g^－1, 明显高于纯相NiO的容量(175 F•g^－1), 并且材料的倍率容量也显著提高.     

外掺Y2O3对镍氢电池正极高温性能的影响

研究了外掺Y2O3对镍氢电池镍正极高温性能的影响. 通常镍正极在高温下放电比容量会骤然降低, 为了提高其高温性能, 进行了球型Ni(OH)2外掺不同比例Y2O3的实验, 对压制的镍电极在不同温度下的充放电情况进行了细致的研究. 研究发现外掺Y2O3的球型Ni(OH)2电极比普通球型Ni(OH)2电极的放电比容量在高温下要高出很多, 在0.2 C充放电情况下外掺1%是最佳比例, 它比普通球型Ni(OH)2电极的放电比容量要高出35%以上, 在1 C充放电情况下外掺0.2%是最佳比例, 它比普通球型Ni(OH)2电极的放电比容量要高出15%以上. 同时对外掺Y2O3提高镍正极放电比容量的原因也进行了初步探讨.     

掺钇纳米NiO的制备及其超大电容性能研究

应用化学共沉淀法制备掺Y的纳米N iO.XRD分析表明,Y的添加不改变N iO的晶体结构,但晶粒尺寸有所减小.利用恒流充放电、循环伏安和交流阻抗等测试方法对Y-N iO电极材料在5 mo.lL-1KOH溶液中作电化学性能测试.结果表明,化学掺杂提高了电极的比容量,当N iO与Y2O3的质量比为1∶0.1时,单电极放电比容量可达到363 F.g-1,比纯氧化镍电极提高了2.02倍.交流阻抗测试显示,Y掺杂降低了电解液在电极中的扩散阻力,提高了质子扩散能力,从而表现了更好的电容性能.     

NiO/MWCNTs复合物的固相合成及其电容性能

本文通过PEG-400辅助室温固相反应制备Ni(OH)2/MWCNTs前驱物,经300℃下热分解得到NiO/MWCNTs复合物。借助X-射线衍射(XRD)和透射电镜(TEM)测试对产物的晶型及形貌进行了表征,采用循环伏安及恒流充放电测试手段对所得复合物的电容性能进行了分析。结果表明,针状NiO较均匀地附着于碳纳米管的表面,当MWCNTs的含量为60%时,NiO/MWCNTs复合物电极的放电比容量得以有效改善,0.2A.g-1下的其放电比容量可达949 F.g-1,远高于纯NiO(422 F.g-1)及MWCNTs(201 F.g-1)的放电比容量,显示了二者的协同效应。     

新型锂离子电池三维结构泡沫NiO电极的制备及电化学性能

通过固相氧化方法,以三维结构泡沫镍为基体和金属镍源,制备了三维结构泡沫氧化镍负极。XRD和SEM结果表明,经500℃氧化处理,泡沫镍基体上形成了NiO微米级的致密活性氧化层。通过充放电测试和循环伏安测试研究了电极的电化学性能,结果表明,三维结构泡沫氧化镍在放电电位区间0.05～3.2VvsLi/Li+,0.2C倍率下充放电,初始容量损失为20%,且经40次循环后,质量比容量为950mAh·g-1,三维泡沫氧化镍电极具有优异的循环容量保持性能。三维泡沫氧化镍具有的大的活性表面积,降低了界面反应的极化,从而提高了NiO电极的倍率放电性能。     

锂离子电池纳米氧化镍负极的制备及应用

应用水热法制备纳米氧化镍,观察样品形貌及研究电极电化学性能.结果表明,在水热合成过程中加入表面活性剂十二烷基硫酸钠（SDS）,可形成疏松多孔、表面呈蜂窝状、颗粒均匀（100～200 nm）的纳米氧化镍.0.1 A/g电流密度下,该纳米NiO电极首周期放电比容量高达2385.7 mAh/g,100周期之后电极比容量仍然稳...     

原位水热法制备NiO纳米电极材料及性能研究

采用原位水热法与高温煅烧相结合,通过镍盐和碱的合成体系直接制备NiO工作电极.利用XRD和SEM对电极结构进行了表征,测试了电化学性能,并对比了3种碱,包括尿素、氨水和氢氧化钠对产物形貌和电化学性能的影响.结果表明以尿素为碱制得的NiO电极以2mol/L的KOH为电解液在0.25A/g的放电电流密度下,获得最大比容量为200F/g.     

铁对快凝稀土系贮氢合金AB5.6微观结构和电化学性能的影响

采用单辊快甩凝固技术制备了过化学计量比稀土系贮氢合金La(NiMn)5.6-xFex (x=0～0.5),研究了Fe及快淬速度对合金电极性能及微观结构的影响. 结果表明,过化学计量比快淬合金的相结构均为过饱和CaCu5单相,且随Fe的增多,合金晶胞体积基本呈线性增加,放电平台压力值递减,合金电极的放电容量增大且电极循环稳定性得到有效提高;当x≥0.4时,合金最大放电容量为341 mAh·g-1,经200次循环后电极容量保持率大于96.2%,1C和2C放电时的HRD分别为88%～89.8%和62%～70%. 不同淬速条件下合金凝固组织形貌和晶态存在明显差别,淬速对合金的电极性能有明显影响;当x=0.3,淬速为10 m·s-1时,合金电极有良好的综合电化学性能.     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.     

Sulfur-directed metal-free and regiospecific methyl C(sp3)–H imidation of thioanisoles

Regiospecific and direct imidation of the methyl C(sp³)–H bond of thioanisoles is realized under mild and metal-free conditions with N-fluorobis(benzenesulfonyl)imide as an oxidant and nitrogen source. Proposed mechanism suggests that thionium ion intermediates and a Pummerer-type reaction are involved. The imidation has advantages such as high step-economy, excellent functionality tolerance, and regiospecificity, giving structurally diverse imidation products.     

Selective syntheses of 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones via temperature-dependent Rh(II)-carbenoid-mediated 2H-azirine-ring expansion

The Rh(II)-catalyzed reaction of 2-carbonyl-substituted 2H-azirines with ethyl 2-cyano-2-diazoacetate or 2-diazo-3,3,3-trifluoropropionate provides an easy access to 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones. These compounds can be selectively prepared from the same starting material using temperature as the only varied parameter. The 2-azabuta-1,3-diene intermediate, a common precursor for both heterocyclic products, isomerizes into 2H-1,3-oxazine under kinetic control, while 1H-pyrrol-3(2H)-one is the sole product of the reaction at elevated temperatures. According to DFT-calculations a one-atom oxazine ring contraction involving ring-opening to a 2-azabuta-1,3-diene intermediate, followed by a 1,5- and 1,2-prototropic shift leads to the consecutive formation of imidoylketene and azomethine ylide, which then further undergo cyclization to the pyrrole derivative.     

Copper catalyzed/mediated synthetic methodology for ebselen and related isoselenazolones

Scope of the copper catalyzed/mediated selenium-nitrogen coupling reaction has been studied for the synthesis of isoselenazolones. It is noticed that the 2-chloro, 2-bromo-, and 2-iodo-aryl amides substrates can be exploited in the selenium-nitrogen coupling reaction by employing 25-100 mol % of CuI/1,10-phenanthroline (L) and potassium carbonate as a base in DMF. Furthermore, electron rich 2-chloro-arylamides also underwent selenium-nitrogen coupling reaction to give biologically important selenium-nitrogen heterocycles. Also, copper-catalyzed selenium-nitrogen coupling reaction has been meticulously applied for the synthesis of diaryl diselenides having methoxy, amine, and amide functionality from respective aryl iodides in the presence of stoichiometric amount of succinimide as an external Se-N coupling partner.     

Knoevenagel condensation catalyzed by novel Nmm-based ionic liquids in water

A series of novel N-methyl morpholine (Nmm) based ionic liquids with 1,2-propanediol group were synthesized and used as catalysts for Knoevenagel condensation at room temperature in water. Under the effect of the catalyst, various aldehydes or aliphatic ketones could react with a wide range of activated methylene compounds well, including malononitrile, alkyl cyanoacetate, cyanoacetamide, β-diketone, barbituric acid, 2-arylacetonitrile and thiazolidinedione. Furthermore, most of the products could be separated just by filtrating and washing with water. Additionally, the catalyst is recyclable and applicable for the large-scale synthesis.     

Construction of polyheterocyclic spirotetrahydrothiophene derivatives via sulfa-Michael/aldol cascade reaction

A series of polyheterocyclic spirotetrahydrothiophene derivatives were obtained in moderate to excellent yields via a catalyst-free sulfa-Michael/aldol cascade reaction of chalcones 1 and commercially available 1,4-dithiane-2,5-diol 2 under mild conditions. We also present the first asymmetric sulfa-Michael/aldol cascade reaction of chalcones 1 and commercially available 1,4-dithiane-2,5-diol 2 with moderate to good enantioselectivities catalyzed by readily available chiral phase-transfer catalysts (PTCs).     

Suzuki-Miyaura reactions of the soluble guanylate cyclase inhibitor NS2028: a non-product specific route to C-8 substituted analogues

Both soluble guanylate cyclase (sGC) inhibitors ODQ 1 and NS2028 2 are synthesized via improved protocols. In the former case treating 3,4-dihydroquinoxalin-2(1H)-one oxime 8, which can be prepared in two steps from 1,2-benzenediamine, with 1,1′-carbonyldiimidazole (CDI) gives the dihydro-ODQ 10 that in the presence of KMnO₄ oxidises to give ODQ 1 in an overall yield of 46% starting from 1,2-benzenediamine. In the latter case, the synthesis affords NS2028 2 from 2-amino-4-bromophenol 3 in three steps with an overall yield of 85% and avoids the need for chromatography. Furthermore, Suzuki-Miyaura reaction conditions are described that enable the preparation of 8-aryl and 8-heteroaryl derivatives of NS2028 directly from NS2028 2. Finally, demethylation of the 8-(methoxyphenyl) substituted analogues afforded the 8-(hydroxyphenyl) derivatives 40-42. All new products are fully characterised.